CN1564347A - Composite positive elelectrode material of lithium ion cell and its prepn. method - Google Patents

Composite positive elelectrode material of lithium ion cell and its prepn. method Download PDF

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CN1564347A
CN1564347A CNA2004100264805A CN200410026480A CN1564347A CN 1564347 A CN1564347 A CN 1564347A CN A2004100264805 A CNA2004100264805 A CN A2004100264805A CN 200410026480 A CN200410026480 A CN 200410026480A CN 1564347 A CN1564347 A CN 1564347A
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lithium
lithium ion
substance
concentration
metal
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周震涛
吕正中
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South China University of Technology SCUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Molecular formula of composite anode material is as following: LiMxFe1-x /(C+M'), where M is Co, Mn, Cr, Ni, Cu, Ag or Au; M' is Co, Mn, Cr, Ni, Cu, Ag or Au, 0<X is less than or equal to 0.2. The method includes steps: preparing sol from materials, deoxidizing metallic ions Mn+ in sol into metal simple substance by using reducing agent; carrying out calcining for dried sol so as to crack organic substance in sol into electro conductive black carbon. Thus, composite anode material LiMxFe1-x /(C+M') is produced. Metal simple substance and black carbon are dispersed in the composite material evenly.

Description

A kind of lithium ion battery composite cathode material and preparation method thereof
Technical field
The invention belongs to technical field of chemical power, more particularly relate to a kind of lithium ion battery composite cathode material and preparation method thereof.
Background technology
LiCoO 2, LiNiO 2, LiMn 2O 4And LiFePO 4All can be used as anode material for lithium-ion batteries.Wherein, LiCoO 2Cost higher, cost an arm and a leg, poor stability, natural resources shortage, toxicity be big; LiNiO 2Preparation difficulty, poor heat stability, fail safe also poor; LiMn 2O 4Though fail safe is better, its specific discharge capacity is lower, and circulating and reversible performance and high-temperature behavior are relatively poor; And olivine-type ferric phosphate (II) lithium (LiFePO 4) plant positive electrode with first three and compare, have low price, nontoxic, abundant raw material, fail safe and Heat stability is good, efficiency for charge-discharge advantages of higher, thereby be with a wide range of applications.
Yet, because LiFePO 4Exist ionic conduction and electron conductivity all lower, Li when discharging and recharging +At LiFePO 4-FePO 4Diffusion coefficient between the two-phase is less, and grain growth is wayward when synthetic waits deficiency, thereby has greatly limited its practical application.At present, the growth that solves the in-problem research of this material and be on the one hand control material crystal grain when synthetic is with the size of control material particle diameter and the ionic conduction of specific area strengthening material, improve the electron conductivity of material by the method for adding the conductive agent (as conductive black) or other transition metal (as manganese, cobalt etc.) that mixes on the other hand, thereby improve the chemical property of material.Reported the employing high temperature solid state reaction as people such as A.Yamada [Journal of The Electrochemical Society, 148 (3), 2001], controlled LiFePO by the control calcining heat 4Grain growth, the crystal grain of gained material is thinner, specific area is bigger, electric conductivity has some improvement; G.Li and A.Yamada[Japan Pat.WO 00/60679 (2000)] reported at preparation LiFePO 4The method of Shi Tianjia carbon black is synthesized LiFePO 4Thereby-C composite material improves its electric conductivity; People such as F.Croce [Electrochemicaland Solid State Letters 5 (3), 2002] have reported at synthetic LiFePO 4The time strengthen its electron conduction with the method for direct doping metals copper or silver powder; And people [Journal ofThe Electrochemical Society, 148 (8), 2001] such as Atsuo Yamada are then by the synthetic Li (Mn of containing transition metal element manganese yFe 1-y) PO 4Improve LiFePO 4Chemical property.
Though the chemical property of material has some improvement, but still also there is following problems in the ferric phosphate that these methods are synthesized (II) lithium composite material:
1. by control LiFePO 4The method of grain growth is not obvious to the improvement of the electric conductivity of material, although because crystal grain diminishes, specific area increases, Li +The evolving path shortened, but electrolyte is at LiFePO 4The possibility that side reaction takes place on the surface has but increased;
2. because the density of carbon black compares LiFePO 4Much smaller, add too much carbon black when synthetic the total body density of material is diminished, thereby make the volumetric specific energy of material that bigger reduction also be arranged;
3. directly the sedimentation of metal dust easily takes place in the technical process of doping metals powder method, and the granularity of powder is difficult to control, thereby makes metal dust at LiFePO 4Skewness in the material has influenced the electrical property of material;
4. containing transition metal (M) element such as manganese or cobalt etc. form Li (M yFe 1-y) PO 4The stability of the crystal structure of material is reduced, thereby influence the electrical property of material.
Summary of the invention
The object of the present invention is to provide a kind of lithium ion battery composite cathode material, described material molecule formula is as follows: LiM xFe 1-xPO 4/ (C+M '), M=Co, Mn, Cr, Ni, Cu, Ag or Au, M '=Co, Mn, Cr, Ni, Cu, Ag or Au, 0＜X≤0.2; The present invention also provides described preparation methods.The method that the present invention adopts liquid-phase reduction and gel solid phase reaction to combine is synthesized this material, specifically is that needed raw material is mixed with colloidal sol, then with reducing agent with the metal ions M in the colloidal sol ' N+Be reduced into metal simple-substance, formed gel after the colloidal sol drying is calcined in inert gas atmosphere, make the organic substance in the gel be cracked into conductive carbon black.Like this, ferric phosphate (II) lithium, metal simple-substance have formed LiM jointly with carbon black xFe 1-xPO 4/ (C+M ') composite material, thus guaranteed that metal simple-substance and carbon black are at composite positive pole LiM xFe 1-xPO 4Be uniformly dispersed among/(C+M ').
Lithium ion battery composite cathode material LiM of the present invention xFe 1-xPO 4The preparation method of/(C+M ') specifically comprises the steps:
(1) phosphate or the phosphoric acid with the lithium salts of solubility or lithium hydroxide, solubility is mixed with the aqueous solution that concentration is 0.50～5.0mol/L respectively; With the nitrate of soluble metal M and metal M ' nitrate (M=Co, Mn, Cr, Ni, Cu, Ag or Au, M '=Co, Mn, Cr, Ni, Cu, Ag or Au, wherein M, M ' can be the same or different) be mixed with the aqueous solution that concentration is 0.05～0.5mol/L respectively; The solubility lithium salts can be lithium nitrate, lithium acetate or their mixture, and soluble phosphate can be ammonium dihydrogen phosphate, diammonium hydrogen phosphate or their mixture;
(2) Li in molar ratio +: PO 4 3-: Mn +: M ' N+=0.80～1.2: 0.80～1.2: 0.008～0.045: 0.008～0.045 proportional sampling batch mixes evenly after, PO in molar ratio again 4 3-: citric acid: the ratio of ethylene glycol=1: 0.05～0.5: 0.05～0.5 adds citric acid and ethylene glycol successively, be stirred to dissolving fully after, Li in molar ratio again +: FeC 2O 42H 2O=1.0: 1.0 ratio adds FeC 2O 42H 2O and in molar ratio the ratio of glucose: M '=1: 0.5～1.5 add glucose, place the boiling water heating and continue to stir 30～150min and must contain PO 4 3-, Li +, M N+, FeC 2O 4With the colloidal sol of metal simple-substance M ', colloidal sol must be contained PO at 60～120 ℃ of following vacuumize 4～8h 4 3-, Li +, M N+, FeC 2O 4Gel with metal simple-substance M ';
(3) gel is put into reactor and placed pit-type furnace feeding nitrogen to protect, heat 4～10h down at 150～350 ℃, cooling must contain PO after grinding 4 3-, Li +, M N+, Fe 2+, metal simple-substance M ' and carbon black the reaction precursor body;
(4) the reaction precursor body is put into reactor and placed pit-type furnace feeding nitrogen to protect, calcine 4～15h down, after the stove cooling, promptly get LiM at 400～700 ℃ xFe 1-xPO 4/ (C+M ') composite positive pole.
The present invention compared with prior art has following advantage:
(1) LiM xFe 1-xPO 4The crystal structure and the pure LiFePO of/(C+M ') composite positive pole 4Crystal structure basic identical;
(2) because at this composite positive pole LiM xFe 1-xPO 4Metal ion (M in/(C+M ') crystal structure N+) (M=Co, Mn, Cr, Ni, Cu, Ag or Au) can strengthening material ionic conducting property, thereby help Li +Embedding take off; And be evenly distributed on LiM xFe 1-xPO 4The nano-level conducting carbon black of grain surface or intergranule and nano scale metal simple substance M ' (M '=Co, Mn, Cr, Ni, Cu, Ag or Au) have strengthened the ionic conducting property and the electronic conductivity of material, so LiM xFe 1-xPO 4The electric conductivity of/(C+M ') composite positive pole is improved;
(3) LiM xFe 1-xPO 4The superior performance of the embedding of/(C+M ') composite positive pole, lithium ionic insertion/deinsertion has higher specific discharge capacity.At room temperature, when 3.0～4.2V, its first discharge specific capacity reaches 167.3mAh/g to this material, is 98% of theoretical specific capacity with 0.2C rate charge-discharge, voltage range; In the time of 60 ℃, its first discharge specific capacity can be up to 169.1mAh/g;
(4) LiM xFe 1-xPO 4The high rate during charging-discharging of/(C+M ') composite positive pole has had significant raising.At room temperature, during with 1C, 3C, 5C rate charge-discharge, its first discharge specific capacity is respectively 162,143,121mAh/g; Under 60 ℃, during with 1C, 3C, 5C rate charge-discharge, its first discharge specific capacity is respectively 167,145,124mAh/g;
(5) LiM xFe 1-xPO 4The cycle charge-discharge reversibility of/(C+M ') composite positive pole is very good.At room temperature, its first discharge specific capacity is 167.3mAh/g, and the specific discharge capacity after 100 charge and discharge cycles is 165.2mAh/g, and capability retention is 98.5%; Under 60 ℃, its first discharge specific capacity is 169.1mAh/g, and the capability retention after 100 circulations is 95%;
(6) because the present invention adopts liquid phase reduction to mix carbon black and metal simple-substance M ' in basis material, so gained LiM xFe 1-xPO 4The tap density front and back of/(C+M ') composite positive pole change very little, therefore adopt doping techniques of the present invention minimum to the influence of the volume energy density of gained material.
Embodiment
The present invention is further illustrated below by embodiment.
Embodiment 1
With LiOH, (NH 4) H 2PO 4, AgNO 3And Co (NO 3) 2Be mixed with the aqueous solution that concentration is 0.5mol/L, 5.0mol/L, 0.05mol/L and 0.05mol/L respectively; The LiOH solution and the 16ml concentration of getting 240ml concentration and be 0.5mol/L are the (NH of 5.0mol/L 4) H 2PO 4After solution mixes, add the AgNO that 20ml concentration is 0.05mol/L more successively 3Solution, 12ml concentration are the Co (NO of 0.05mol/L 3) 2Solution, the 0.005mol citric acid, 0.005mol ethylene glycol after treating to dissolve fully, adds 0.12molFeC again 2O 42H 2O and 0.0015mol glucose place the boiling water heating and continue promptly to get colloidal sol behind the stirring 30min, and colloidal sol is got gel at 120 ℃ of following vacuumize 4h; Gel is placed pit-type furnace, feed nitrogen and protect, at 150 ℃ of heating 8h, cooling must contain PO after grinding 4 3-, Li +, Co 2+, Fe 2+, metal simple-substance Ag and carbon black the reaction precursor body; The reaction precursor body is placed pit-type furnace, feed nitrogen and protect, be warming up to 700 ℃ of constant temperature 4h, after the stove cooling, promptly get sample.
Make cathode film with the gained sample as positive active material, cathode film consist of m Active material: m Acetylene black: m Polytetrafluoroethylene=80: 15: 5, thickness≤0.1mm made positive plate with the cathode film roll extrusion on stainless (steel) wire; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard2300); Electrolyte is 1mol/LLiPF 6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1: 1) is assembled into Experimental cell in the glove box of applying argon gas.The result who carries out charge-discharge test with the 0.2C multiplying power is as follows: at room temperature, the first discharge specific capacity of material is 132.7mAh/g, and the capability retention after 100 circulations is 86.4%; Under 60 ℃, the first discharge specific capacity of material is 138.3mAh/g, and the capability retention after 100 circulations is 81.3%.
Embodiment 2
With LiNO 3, H 3PO 4, AgNO 3And Ni (NO 3) 2Be mixed with the aqueous solution that concentration is 5mol/L, 0.5mol/L, 0.5mol/L and 0.5mol/L respectively; Get the LiNO that 16ml concentration is 5mol/L 3Solution and 240ml concentration are the H of 0.5mol/L 3PO 4After solution mixes, add the AgNO that 10ml concentration is 0.5mol/L more successively 3Solution, 8ml concentration are the Ni (NO of 0.5mol/L 3) 2Solution, the 0.05mol citric acid, 0.05mol ethylene glycol after treating to dissolve fully, adds 0.08molFeC again 2O 42H 2O and 0.0025mol glucose place the boiling water heating and continue promptly to get colloidal sol behind the stirring 150min, and colloidal sol is got gel at 60 ℃ of following vacuumize 8h; Again gel is placed pit-type furnace, feed nitrogen and protect, at 350 ℃ of heating 10h, cooling must contain PO after grinding 4 3-, Li +, Ag +, Fe 2+, metal simple-substance Ni and carbon black the reaction precursor body; The reaction precursor body is placed pit-type furnace, feed nitrogen and protect, be warming up to 400 ℃ of constant temperature 15h, after the stove cooling, promptly get sample.
Make cathode film with the gained sample as positive active material, cathode film consist of m Active material: m Acetylene black: m Polytetrafluoroethylene=80: 15: 5, thickness≤0.1mm made positive plate with the cathode film roll extrusion on stainless (steel) wire; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard2300); Electrolyte is 1mol/LLiPF 6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1: 1) is assembled into Experimental cell in the glove box of applying argon gas.The result who carries out charge-discharge test with the 0.2C multiplying power is as follows: at room temperature, the first discharge specific capacity of material is 112.8mAh/g, and the capability retention after 100 circulations is 75.5%; Under 60 ℃, the first discharge specific capacity of material is 126.6mAh/g, and the capability retention after 100 circulations is 71.4%.
Embodiment 3
With CH 3COOLi, LiNO 3, (NH 4) 2HPO 4, (NH 4) H 2PO 4, AgNO 3And Cu (NO 3) 2Be mixed with the aqueous solution that concentration is 1.0mol/L, 1.0mol/L, 1.0mol/L, 1.0mol/L, 0.15mol/L and 0.1mol/L respectively; Get the CH that 50ml concentration is 1.0mol/L 3COOLi solution, 50ml concentration are the LiNO of 1.0mol/L 3Solution, 50ml concentration are the (NH of 1.0mol/L 4) 2HPO 4Solution and 50ml concentration are the (NH of 1.0mol/L 4) H 2PO 4After solution mixes, add the AgNO that 10ml concentration is 0.15mol/L more successively 3Solution, 10ml concentration are the Cu (NO of 0.1mol/L 3) 2Solution, the 0.015mol citric acid, 0.015mol ethylene glycol after treating to dissolve fully, adds 0.1molFeC again 2O 42H 2O and 0.0015mol glucose place the boiling water heating and continue promptly to get colloidal sol behind the stirring 60min, and colloidal sol is got gel at 80 ℃ of following vacuumize 6h; Again gel is placed pit-type furnace, feed nitrogen and protect, at 250 ℃ of heating 6h, cooling must contain PO after grinding 4 3-, Li +, Cu 2+, Fe 2+, metal simple-substance Ag and carbon black the reaction precursor body; The reaction precursor body is placed pit-type furnace, feed nitrogen and protect, be warming up to 500 ℃ of constant temperature 12h, after the stove cooling, promptly get sample.
Make cathode film with the gained sample as positive active material, cathode film consist of m Active material: m Acetylene black: m Polytetrafluoroethylene=80: 15: 5, thickness≤0.1mm made positive plate with the cathode film roll extrusion on stainless (steel) wire; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard2300); Electrolyte is 1mol/LLiPF 6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1: 1) is assembled into Experimental cell in the glove box of applying argon gas.The result who carries out charge-discharge test with the 0.2C multiplying power is as follows: at room temperature, the first discharge specific capacity of material is 145.6mAh/g, and the capability retention after 100 circulations is 87.5%; Under 60 ℃, the first discharge specific capacity of material is 148.3mAh/g, and the capability retention after 100 circulations is 71.5%.
Embodiment 4
With CH 3COOLi, (NH 4) 2HPO 4And AgNO 3Be mixed with the aqueous solution that concentration is 1.0mol/L, 1.0mol/L and 0.2mol/L respectively; Get the CH that 100ml concentration is 1.0mol/L 3COOLi solution and 100ml concentration are the (NH of 1.0mol/L 4) 2HPO 4After solution mixes, add the AgNO that 10ml concentration is 0.2mol/L more successively 3Solution, the 0.015mol citric acid, 0.015mol ethylene glycol after treating to dissolve fully, adds 0.1molFeC again 2O 42H 2O and 0.0012mol glucose place the boiling water heating and continue promptly to get colloidal sol behind the stirring 60min, and colloidal sol is got gel at 80 ℃ of following vacuumize 6h; Again gel is placed pit-type furnace, feed nitrogen and protect, at 250 ℃ of heating 4h, cooling must contain PO after grinding 4 3-, Li +, Ag +, Fe 2+, metal simple-substance Ag and carbon black the reaction precursor body; The reaction precursor body is placed pit-type furnace, feed nitrogen and protect, be warming up to 500 ℃ of constant temperature 12h, after the stove cooling, promptly get sample.
Make cathode film with the gained sample as positive active material, cathode film consist of m Active material: m Acetylene black: m Polytetrafluoroethylene=80: 15: 5, thickness≤0.1mm made positive plate with the cathode film roll extrusion on stainless (steel) wire; With metal lithium sheet as negative pole; Barrier film is import microporous polypropylene membrane (Celgard2300); Electrolyte is 1mol/LLiPF 6/ ethylene carbonate (EC)+dimethyl carbonate (DMC) (volume ratio 1: 1) is assembled into Experimental cell in the glove box of applying argon gas.The result who carries out charge-discharge test with the 0.2C multiplying power is as follows: at room temperature, the first discharge specific capacity of material is 165.4mAh/g, and the capability retention after 100 circulations is 98.5%; Under 60 ℃, the first discharge specific capacity of material is 168.1mAh/g, and the capability retention after 100 circulations is 95%.And with pure LiFePO 4Use the same method as positive active material and to make Experimental cell, (0.2C) compares test with same charge-discharge magnification, its result is: at room temperature, the first discharge specific capacity of this material is 130.7mAh/g, and the capability retention after 100 circulations is 87.5%; Under 60 ℃, its first discharge specific capacity is 135.4mAh/g, and the capability retention after 100 circulations is 79.3%.
As seen, with the prepared composite positive pole LiM of preparation method of the present invention xFe 1-xPO 4/ (C+M '), electric conductivity height not only, the superior performance of embedding, lithium ionic insertion/deinsertion has higher specific discharge capacity, and the cycle charge-discharge reversibility is good, is applicable to the positive electrode of making lithium ion battery.

Claims (4)

1. the composite positive pole of a lithium ion battery is characterized in that its molecular formula is as follows:
LiM xFe 1-xPO 4/(C+M′)
Wherein, M is Co, Mn, Cr, Ni, Cu, Ag or Au, and M ' is Co, Mn, Cr, Ni, Cu, Ag or Au, 0＜X≤0.2.
2. the preparation method of lithium ion battery composite cathode material according to claim 1 is characterized in that concrete preparation process is as follows:
(1) phosphate or the phosphoric acid with the lithium salts of solubility or lithium hydroxide, solubility is mixed with the aqueous solution that concentration is 0.50～5.0mol/L respectively; With the nitrate of soluble metal M and metal M ' nitrate be mixed with the aqueous solution that concentration is 0.05～0.5mol/L respectively;
(2) Li in molar ratio +: PO 4 3-: Mn +: M ' N+=0.80～1.2: 0.80～1.2: 0.008～0.045: 0.008～0.045 proportional sampling batch mixes evenly after, PO in molar ratio again 4 3-: citric acid: the ratio of ethylene glycol=1: 0.05～0.5: 0.05～0.5 adds citric acid and ethylene glycol successively, be stirred to dissolving fully after, Li in molar ratio again +: FeC 2O 42H 2O=1.0: 1.0 ratio adds FeC 2O 42H 2O and in molar ratio the ratio of glucose: M '=1: 0.5～1.5 add glucose, place the boiling water heating and continue to stir 30～150min and must contain PO 4 3-, Li +, Mn +, FeC 2O 4With the colloidal sol of metal simple-substance M ', colloidal sol must be contained PO at 60～120 ℃ of following vacuumize 4～8h 4 3-, Li +, Mn +, FeC 2O 4Gel with metal simple-substance M ';
(3) gel is put into reactor and placed pit-type furnace feeding nitrogen to protect, heat 4～10h down at 150～350 ℃, cooling must contain PO after grinding 4 3-, Li +, Mn +, Fe 2+, metal simple-substance M ' and carbon black the reaction precursor body;
(4) the reaction precursor body is put into reactor and placed pit-type furnace feeding nitrogen to protect, calcine 4～15h down, after the stove cooling, promptly get LiM at 400～700 ℃ xFe 1-xPO 4/ (C+M ') composite positive pole.
3. the preparation method of lithium ion battery composite cathode material according to claim 2 is characterized in that described solubility lithium salts is lithium nitrate or lithium acetate or their mixture.
4. the preparation method of lithium ion battery composite cathode material according to claim 2 is characterized in that described soluble phosphate is ammonium dihydrogen phosphate or diammonium hydrogen phosphate or their mixture.
CNA2004100264805A 2004-03-15 2004-03-15 Composite positive elelectrode material of lithium ion cell and its prepn. method Pending CN1564347A (en)

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100420076C (en) * 2005-12-19 2008-09-17 南开大学 Synthesis of lithium ion battery anode material vanadium lithium phosphate using sol-gel method
CN101375439B (en) * 2006-02-14 2012-08-08 陶氏环球技术公司 Lithium phosphate manganese anode material for lithium secondary battery
CN102867959A (en) * 2012-10-17 2013-01-09 中南大学 Anode LiV3O8/Ag composite material of lithium ion battery and manufacture method thereof
CN101901898B (en) * 2009-12-07 2013-02-06 耿世达 Lithium battery LiFePO4 anode material with internal three-dimensional conductive structure and preparation method thereof
CN103229343A (en) * 2010-12-02 2013-07-31 索尼公司 Solid electrolyte cell and positive electrode active material
CN103700852A (en) * 2009-03-19 2014-04-02 台湾立凯电能科技股份有限公司 Composition for use in electrochemical redox reaction and battery including the same
CN104835985A (en) * 2015-03-24 2015-08-12 江苏乐能电池股份有限公司 A preparing method of a high-specific-energy lithium ion battery
WO2023226556A1 (en) * 2022-05-25 2023-11-30 广东邦普循环科技有限公司 Preparation method for and use of lithium iron phosphate

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100420076C (en) * 2005-12-19 2008-09-17 南开大学 Synthesis of lithium ion battery anode material vanadium lithium phosphate using sol-gel method
CN101375439B (en) * 2006-02-14 2012-08-08 陶氏环球技术公司 Lithium phosphate manganese anode material for lithium secondary battery
CN103700852A (en) * 2009-03-19 2014-04-02 台湾立凯电能科技股份有限公司 Composition for use in electrochemical redox reaction and battery including the same
CN101901898B (en) * 2009-12-07 2013-02-06 耿世达 Lithium battery LiFePO4 anode material with internal three-dimensional conductive structure and preparation method thereof
CN103229343A (en) * 2010-12-02 2013-07-31 索尼公司 Solid electrolyte cell and positive electrode active material
CN102867959A (en) * 2012-10-17 2013-01-09 中南大学 Anode LiV3O8/Ag composite material of lithium ion battery and manufacture method thereof
CN102867959B (en) * 2012-10-17 2015-04-22 中南大学 Anode LiV3O8/Ag composite material of lithium ion battery and manufacture method thereof
CN104835985A (en) * 2015-03-24 2015-08-12 江苏乐能电池股份有限公司 A preparing method of a high-specific-energy lithium ion battery
WO2023226556A1 (en) * 2022-05-25 2023-11-30 广东邦普循环科技有限公司 Preparation method for and use of lithium iron phosphate
GB2622170A (en) * 2022-05-25 2024-03-06 Guangdong Brunp Recycling Technology Co Ltd Preparation method for and use of lithium iron phosphate

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